EP1220878A1 - Self-sealing silicones fluids - Google Patents
Self-sealing silicones fluidsInfo
- Publication number
- EP1220878A1 EP1220878A1 EP00955702A EP00955702A EP1220878A1 EP 1220878 A1 EP1220878 A1 EP 1220878A1 EP 00955702 A EP00955702 A EP 00955702A EP 00955702 A EP00955702 A EP 00955702A EP 1220878 A1 EP1220878 A1 EP 1220878A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- fluid
- self
- silicone
- elastomeric
- elastomeric silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001296 polysiloxane Polymers 0.000 title claims abstract description 82
- 239000012530 fluid Substances 0.000 title claims abstract description 79
- 238000007789 sealing Methods 0.000 title claims abstract description 25
- 239000002245 particle Substances 0.000 claims abstract description 51
- 239000000203 mixture Substances 0.000 claims abstract description 10
- -1 polysiloxane Polymers 0.000 claims description 43
- 238000000034 method Methods 0.000 claims description 8
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 239000000853 adhesive Substances 0.000 claims description 6
- 230000001070 adhesive effect Effects 0.000 claims description 6
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052710 silicon Inorganic materials 0.000 claims 2
- 239000010703 silicon Substances 0.000 claims 2
- 238000009826 distribution Methods 0.000 abstract description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 235000013870 dimethyl polysiloxane Nutrition 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- XMSXQFUHVRWGNA-UHFFFAOYSA-N Decamethylcyclopentasiloxane Chemical compound C[Si]1(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O[Si](C)(C)O1 XMSXQFUHVRWGNA-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000012935 Averaging Methods 0.000 description 2
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000004970 Chain extender Substances 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 150000004819 silanols Chemical class 0.000 description 1
- 229920002379 silicone rubber Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K3/00—Materials not provided for elsewhere
- C09K3/10—Materials in mouldable or extrudable form for sealing or packing joints or covers
- C09K3/1006—Materials in mouldable or extrudable form for sealing or packing joints or covers characterised by the chemical nature of one of its constituents
- C09K3/1018—Macromolecular compounds having one or more carbon-to-silicon linkages
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/163—Sealing compositions or agents, e.g. combined with propellant agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C73/00—Repairing of articles made from plastics or substances in a plastic state, e.g. of articles shaped or produced by using techniques covered by this subclass or subclass B29D
- B29C73/16—Auto-repairing or self-sealing arrangements or agents
- B29C73/22—Auto-repairing or self-sealing arrangements or agents the article containing elements including a sealing composition, e.g. powder being liberated when the article is damaged
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
Definitions
- the invention relates to a self-sealing container system comprising a wall, a polysiloxaiie fluid and a silicone composition having a unique particle size distribution useful as a self-sealing agent for silicone fluid applications.
- Elastomeric polysiloxane particles are produced using a wide variety of methods known in the art. Examples of patents on the preparation of elastomeric polysiloxanes include: U.S. 4,970,252, U.S. 5,760,116, U.S. 4,340,709, U.S. 3,436,366, U.S. 5,654,362, U.S. 4,172,101, U.S. 5,811,487, U.S. 5,880,210 and U.S. 5,987,169.
- a self-sealing fluid container system which comprises:
- the container may additionally comprise a substantially continuous adhesive seal wherein the seal contains the fluid.
- the container system may also be such that the inner surface defines a volume, and the fluid is contained within the volume, for example, in a bag.
- substantially continuous means no breaks, tears, holes or punctures that are measurable.
- the self -sealing container system can be any container comprising walls that are impermeable to fluids and have inner and outer surfaces.
- the walls may be rigid or flexible, although flexible walls that bend and are adaptable to different shapes are preferred.
- the wall thickness is not important, although walls that are at least 0.001 inches in thickness are preferred. Examples of materials used in the construction of the containers are: urethane, polypropylene, polyethylene, and various high performance engineered thermoplastics.
- These containers occasionally have small holes in them that are the result of the manufacturing process, some force on the wall that creates a hole extending from the inner surface to the outer surface, or small breaks or discontinuities in the adhesive seal of the container, through which fluid can flow. The holes are sometimes created during the filling of the containers, during routine manufacturing operations or during normal wear and abuse depending on the application.
- the elastomeric silicone particles of the present invention comprise from about 0.2 to about 95 percent by weight, more preferably from about 0.5 to about 50 percent and even more preferably from about 1 to about 10 percent, of the total silicone fluid compound, depending on the desired fluid viscosity.
- the particle size of the elastomeric particles used in the composition are from about 50 to about 1000 microns, more preferably from about 60 to about 500 microns and even more preferably from about 80 to about 300 microns, depending on the size of the hole to be filled.
- elastomeric silicone or “elastomeric polysiloxane” refers to crosslinked polysiloxanes.
- Elastomeric polysiloxanes are made by known methods either neat, in situ or in an alternative solvent through polymerization and/ or crosslinking of silicone components, potentially employing silicone or organic crosslinkers or chain extenders in conjunction with other silicone components, such as, for example, hydrosilylation polymerization of vinyl and hydridosiloxanes, either as homogeneous solutions or emulsions; condensation of silanols, alkoxysiloxanes or carboxysiloxanes; and free radical polymerization.
- the elastomeric polysiloxane is prepared through hydrosilylation of a vinyl terminated siloxane with a silylhydride as crosslinking component, with a platinum catalyst in the presence of a cyclic siloxane solvent.
- the vinyl terminated siloxane is divinylpolysiloxane
- the silylhydride is an MHQ resin averaging eight SiH units per molecule
- the cyclic siloxane solvent is decamethy ley clopentasiloxane .
- the elastomeric polysiloxane may be reduced to a desired particle size through grinding, milling or any other form of particle shear known in the art.
- the elastomeric polysiloxane particles of the present invention can be added to a desired silicone fluid, where they are dispersed throughout the silicone fluid.
- the elastomeric silicone particles must be insoluble in the polysiloxane fluid, they must be solid particles, and they must remain suspended or dispersed in the fluid.
- the terms "suspended” or “dispersed” mean that the elastomeric polysiloxane particles are uniformly spread throughout the liquid and do not settle out. In order to remain dispersed or suspended, the particles are preferably of a density that is compatible with the fluid to be used.
- the elastomeric particles are used to self-seal small leaks in applications where a sealed container may develop a small leak during production, filling or normal application, thus preventing the loss of fluid from the container. This will prevent rejection or failure of the containers.
- the elastomeric particles are generally smaller than the hole or break to be filled. In a preferred embodiment, the particles are approximately one-third the width of the diameter of the hole or break. In a highly preferred embodiment, the particle size of the elastomeric silicone particles is from about 50 to about 1000 microns, and the amount of the elastomeric particles dispersed in the fluid is from about 0.2 to about 10 weight percent.
- silicone fluid means a polysiloxane fluid.
- the polysiloxane fluid may be any polysiloxane fluid that is compatible with the elastomeric silicone particles.
- Preferred polysiloxane fluids include: cyclicpolydimethylsiloxanes, cyclicpolydiphenylsiloxanes, polydimethylsiloxane, polymethylphenylsiloxanes, polydiphenylsiloxanes, alkyl substituted polydimethylsiloxane, polyether substituted siloxanes, alkoxy substituted polydimethylsiloxanes.
- the silicone fluid is polydimethylsiloxane, and the viscosity range of the fluid is 0.5 to 750,000 centistokes.
- Another aspect of the present invention is a self-sealing silicone fluid composition
- a self-sealing silicone fluid composition comprising:
- R and R 1 are each one to ten carbon atom monovalent hydrocarbon radicals, and 'n' is an integer from 0 to 500,000 whereby the viscosity of the polysiloxane fluid is from about 0.5 centistokes to about 750,000 centistokes at 25°C; and
- Another aspect of the present invention is a method for making a self- sealing fluid comprising:
- the self-sealing container system of the present invention may be incorporated into other systems, or used alone, where the need to seal small holes in the container is important.
- Articles may be formed comprising: a self-sealing container system comprising:
- the self-sealing container system may additionally be a system wherein the inner surface defines a volume, and the fluid is contained within the volume, for example, in a bag, a container holding an electronic control board or other container in which the fluid is completely contained.
- the article formed by the self-sealing container may also be such that the inner surface defines a volume and the fluid is contained within the volume.
- a self-sealing container is a modular housing for an automotive electronic control module.
- Self-sealing silicone fluids are particularly useful in electronic applications because they provide the desirable characteristics necessary for electronic component protection, such as moisture and contamination protection, flowability into small areas, good insulating properties and excellent heat transfer. Because the silicone fluid is self-sealing, small holes or cracks in the housing module or gaps in the gasket are automatically sealed and liquid is prevented from flowing out of the housing.
- the respective elastomeric polysiloxane particles of and Examples 1 and 2 of the present invention were each prepared through the hydrosilylation of a vinyl terminated siloxane (divinylpol siloxane) with a MHQ silylhydride resin as a crosslinking component, using Karstedt's platinum catalyst in the presence of a cyclic siloxane solvent (decamethylcyclopentasiloxane). Divinylpoly siloxane was blended with the silylhydride in decamethylcyclopentasiloxane. The platinum catalyst was added and the reaction stirred and heated to 80°C to allow reaction and curing.
- the resulting material was diluted to 5.5 weight % elastomer content using polydimethylsiloxane having a viscosity of approximately 5 centistokes, and it was then subjected to shear using a Sonolator to obtain the desired particle size, as measured by a Malvern Particle Size analyzer (with the sample diluted in decamethylcyclopentasiloxane and isopropyl alcohol).
- Example 1 The material in Example 1 was further diluted in polydimethylsiloxane having a viscosity of approximately 1000 centistokes to reach the desired final concentration of elastomeric silicone in the fluid. Approximately 300 grams of the material was added to a polyethylene plastic bag. A pinhole leak was put into the bag. Leakage was measured over a 14 day period.
- Example 2 The material in Example 2 was produced in a similar manner as that of Example 1. It was diluted to the desired final concentration of elastomeric silicone particles in decamethylcyclopentasiloxane, with the desired particle size. One quart of the material was placed in a sealable polyethylene plastic bag. A 0.062 inch diameter hole was punched in the bag. Leakage was measured over a 30 day period.
- a comparative test was run using the same test used in examples 1 and 2.
- Polydimethylsiloxane having a viscosity of approximately 1000 centistokes with no elastomeric silicone particles in the fluid was added to a urethane bag with a 1 millimeter diameter puncture hole in the bag to a height of at least one inch above the hole. Leakage was measured over a 24 hour period, and slightly over 3 grams of fluid leaked from the bag.
- the fluid loss for the same test using a fluid with elastomeric silicone particles was less than 1 gram over a 14 day and 30 day period.
- Example 1 had a lower concentration of elastomeric particles having a larger particle size than the particles of Example 2.
- the comparative example had no particles; only a silicone fluid was in the bag.
- a modular housing used for automotive electronic control modules was tested with the self-sealing silicone fluid of the present invention.
- a 1 mm hole was drilled in the housing, and the housing was then filled with a self-sealing silicone fluid (1% silicone elastomer in 1000 centistokes silicone fluid, as prepared above). After an initial drop of fluid due to direct pouring, the silicone fluid sealed the hole in the housing and no further silicone fluid passed through the hole.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Containers And Packaging Bodies Having A Special Means To Remove Contents (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US15032199P | 1999-08-23 | 1999-08-23 | |
| US150321P | 1999-08-23 | ||
| PCT/US2000/022704 WO2001014476A1 (en) | 1999-08-23 | 2000-08-18 | Self-sealing silicones fluids |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| EP1220878A1 true EP1220878A1 (en) | 2002-07-10 |
| EP1220878B1 EP1220878B1 (en) | 2006-08-02 |
Family
ID=22534026
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP00955702A Expired - Lifetime EP1220878B1 (en) | 1999-08-23 | 2000-08-18 | Self-sealing silicones fluids |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1220878B1 (en) |
| JP (1) | JP2003507279A (en) |
| DE (1) | DE60029808T2 (en) |
| WO (1) | WO2001014476A1 (en) |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0655897B2 (en) * | 1988-04-22 | 1994-07-27 | 信越化学工業株式会社 | Method for producing silicone composition |
| US5654362A (en) * | 1996-03-20 | 1997-08-05 | Dow Corning Corporation | Silicone oils and solvents thickened by silicone elastomers |
| US5760116A (en) * | 1996-09-05 | 1998-06-02 | General Electric Company | Elastomer gels containing volatile, low molecular weight silicones |
| US5854336A (en) * | 1997-03-20 | 1998-12-29 | Chesebrough-Pond's Usa Co., Division Of Conopco, Inc. | Process for preparing silicone elastomer compositions |
| US5929162A (en) * | 1997-12-12 | 1999-07-27 | General Electric Company | Elastomer dispersion having a unique particle size distribution |
| US6237333B1 (en) * | 1998-04-08 | 2001-05-29 | The B. F. Goodrich Company | Microgel disersion for hydraulic apparatus and processes |
-
2000
- 2000-08-18 DE DE60029808T patent/DE60029808T2/en not_active Expired - Fee Related
- 2000-08-18 JP JP2001518796A patent/JP2003507279A/en not_active Withdrawn
- 2000-08-18 WO PCT/US2000/022704 patent/WO2001014476A1/en not_active Ceased
- 2000-08-18 EP EP00955702A patent/EP1220878B1/en not_active Expired - Lifetime
Non-Patent Citations (1)
| Title |
|---|
| See references of WO0114476A1 * |
Also Published As
| Publication number | Publication date |
|---|---|
| DE60029808T2 (en) | 2007-03-01 |
| JP2003507279A (en) | 2003-02-25 |
| WO2001014476A1 (en) | 2001-03-01 |
| DE60029808D1 (en) | 2006-09-14 |
| EP1220878B1 (en) | 2006-08-02 |
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